title: Gas-phase fragmentation of deprotonated p-hydroxyphenacyl derivatives.
abstract: Electrospray ionization of methanolic solutions of p-hydroxyphenacyl derivatives HO-C(6)H(4)-C(O)-CH(2)-X (X = leaving group) provides abundant signals for the deprotonated species which are assigned to the corresponding phenolate anions (-)O-C(6)H(4)-C(O)-CH(2)-X. Upon collisional activation in the gas phase, these anions inter alia undergo loss of a neutral "C(8)H(6)O(2)" species concomitant with formation of the corresponding anions X(-). The energies required for the loss of the neutral roughly correlate with the gas phase acidities of the conjugate acids (HX). Extensive theoretical studies performed for X = CF(3)COO in order to reveal the energetically most favorable pathway for the formation of neutral "C(8)H(6)O(2)" suggest three different routes of similar energy demands, involving a spirocyclopropanone, epoxide formation, and a diradical, respectively.
authors.affiliation: Department of Organic Chemistry, Faculty of Sciences, Charles University in Prague, Hlavova 8, 12083 Prague 2, Czech Republic.
authors.forename: Marek
authors.initials: M
authors.lastname: Remeš
authors.forename: Jana
authors.initials: J
authors.lastname: Roithová
authors.forename: Detlef
authors.initials: D
authors.lastname: Schröder
authors.forename: Elizabeth D
authors.initials: ED
authors.lastname: Cope
authors.forename: Chamani
authors.initials: C
authors.lastname: Perera
authors.forename: Sanjeewa N
authors.initials: SN
authors.lastname: Senadheera
authors.forename: Kenneth
authors.initials: K
authors.lastname: Stensrud
authors.forename: Chi-cheng
authors.initials: CC
authors.lastname: Ma
authors.forename: Richard S
authors.initials: RS
authors.lastname: Givens
mesh_terms: D000098:Acetophenones / Q000737:chemistry*; D000838:Anions / Q000737:chemistry*; D003521:Cyclopropanes / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D008962:Models, Theoretical; D015394:Molecular Structure; D005741:Noble Gases / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013141:Spiro Compounds / Q000737:chemistry*
chemical_list: D000098:Acetophenones; D000838:Anions; D003521:Cyclopropanes; D004852:Epoxy Compounds; D005741:Noble Gases; D012996:Solutions; D013141:Spiro Compounds